Chlorite alteration in aqueous solutions and uranium removal by altered chlorite.

Chlorite alteration and the U removal capacity of altered chlorite were investigated. Batch kinetic dissolution tests using clinochlore CCa-2 were conducted for 60days in aqueous solutions of various pHs and ionic strengths. Batch sorption tests using these altered chlorite samples were conducted for 48h with natural groundwater containing 3.06×10-6M U. Chlorite dissolution was influenced more by pHo than by the ionic strength of the solution. TEM analysis revealed Fe(oxy)hydroxide aggregates in the solid residue from the batch dissolution test with 0.1M NaClO4 solution at pHo=10. The U removal capacity of the reacted chlorite samples at pHo=6-10 was higher than that of the reacted chlorite samples at pHo=3. The degree of dissolution of chlorite samples reacted at pHo=3-8 was inversely proportional to the U removal capacity, but that of chlorite samples reacted at pHo=10 was proportional to the U removal capacity. The positive correlation between the U removal capacity and degree of chlorite dissolution at pHo=10 might be due to the formation of Fe-containing secondary minerals and changes in the reactive sites.

Appropriate Domain Size for Groundwater Flow Modeling with a Discrete Fracture Network Model.

When a discrete fracture network (DFN) is constructed from statistical conceptualization, uncertainty in simulating the hydraulic characteristics of a fracture network can arise due to the domain size. In this study, the appropriate domain size, where less significant uncertainty in the stochastic DFN model is expected, was suggested for the Korea Atomic Energy Research Institute Underground Research Tunnel (KURT) site. The stochastic DFN model for the site was established, and the appropriate domain size was determined with the density of the percolating cluster and the percolation probability using the stochastically generated DFNs for various domain sizes. The applicability of the appropriate domain size to our study site was evaluated by comparing the statistical properties of stochastically generated fractures of varying domain sizes and estimating the uncertainty in the equivalent permeability of the generated DFNs. Our results show that the uncertainty of the stochastic DFN model is acceptable when the modeling domain is larger than the determined appropriate domain size, and the appropriate domain size concept is applicable to our study site.

Effect of Cr(VI) concentration on gas and particle production during iron oxidation in aqueous solutions containing Cl- ions.

Zero-valent iron (ZVI) is commonly used as a medium in permeable reactive barriers (PRBs) because of its high reducing ability. The generation of H2 gas in PRBs, however, can decrease the permeability of PRBs and reduce the contact area between the PRB and contaminated groundwater. This study investigated the effect of the initial Cr(VI) concentration ([Cr(VI)init]) in aqueous solutions containing Cl- ions on the generation of H2 gas. ZVI chips were reacted in reactors with 0.5-M NaCl solutions with [Cr(VI)init] ranging between 51 and 303 mg/L. The initial pH was set at 3. The oxidation of ZVI chips by Cr(VI) in aqueous solutions containing Cl- ions produced H2 gas and particles (Fe(III)-Cr(III)(oxy)hydroxides). The Cr(VI) removal from aqueous solutions increased as the [Cr(VI)init] increased, as did H2 gas generation. The positive effect of [Cr(VI)init] on H2 gas generation might be due to an increase in the redox potential gradient as [Cr(VI)init] increases. This increased gradient would enhance H+ ion penetration through the passive film (Fe(III)-Cr(III)(oxy)hydroxides), which formed on the ZVI surface, by diffusion from the solution to pits beneath the passive film.

Derivative-assisted classification of fractured zones crossing a deep borehole.

In this study, the derivative analysis using the derivative of drawdown with respect to log-time was utilized to determine candidates for hydraulic conductor domains (HCDs). At a 500-m deep borehole in the study site, the fractured rocks crossing the borehole were first classified in fractured and nonfractured zones by core logging and geophysical loggings, such as acoustic televiewing, density, and flow loggings. After conducting the hydraulic tests such as constant head withdrawal and recovery tests at the fractured zones and the nonfractured zones, the derivative analyses were carried out, of which the results were evaluated to determine the candidates for HCDs. For the nonfractured zones, the diagnostic plot has only a big hump indicating poor connection of the background fractures to the permeable geologic media, while those of the candidates for HCDs show various flow regimes. On the basis of these results, the candidates for HCDs among the fractured zones were determined. From discussion on the results, the combination of the spacing analysis and derivative analysis following a hydraulic test is recommended for determining the candidates for HCDs rather than other geophysical loggings.

Influence of pressure change during hydraulic tests on fracture aperture.

In a series of field experiments, we evaluate the influence of a small water pressure change on fracture aperture during a hydraulic test. An experimental borehole is instrumented at the Korea Atomic Energy Research Institute (KAERI) Underground Research Tunnel (KURT). The target fracture for testing was found from the analyses of borehole logging and hydraulic tests. A double packer system was developed and installed in the test borehole to directly observe the aperture change due to water pressure change. Using this packer system, both aperture and flow rate are directly observed under various water pressures. Results indicate a slight change in fracture hydraulic head leads to an observable change in aperture. This suggests that aperture change should be considered when analyzing hydraulic test data from a sparsely fractured rock aquifer.

Fluorine geochemistry in bedrock groundwater of South Korea.

High fluoride concentrations (median=4.4 mg/L) in deep bedrock groundwater of South Korea prevent the usage of it as a drinking water source. The hydrogeochemistry of deep thermal groundwaters (N=377) in diverse bedrocks has been studied in order to evaluate the geologic and geochemical controls on fluoride concentrations in groundwater. The groundwater samples were clustered geologically, and the average and median concentrations of fluoride were compared by the Mann-Whitney U test. The order of median fluoride concentration with respect to geology is as follows: metamorphic rocks> or =granitoids > or =complex rock>>volcanic rocks> or =sedimentary rocks. This result indicates that the geological source of fluoride in groundwater is related to the mineral composition of metamorphic rocks and granitoids. With respect to groundwater chemistry, the fluoride concentration was highest in Na-HCO3 type groundwater and lowest in Ca-HCO3 type groundwater. Ionic relationships also imply that the geochemical behavior of fluoride in groundwater is related to the geochemical process releasing Na and removing Ca ions. The thermodynamic relationship between the activities of Ca and F indicates that fluoride concentration is controlled by the equilibrium of fluorite (CaF2). In other words, the upper limits of fluoride concentration are determined by the Ca ion; i.e., Ca concentrations play a crucial role in fluoride behavior in deep thermal groundwater. The result of this study suggests that the high fluoride in groundwater originates from geological sources and fluoride can be removed by fluorite precipitation when high Ca concentration is maintained. This provides a basis for a proper management plan to develop the deep thermal groundwater and for treatment of high fluoride groundwater frequently found in South Korea.

In-situ electrochemical measurements of total concentration and speciation of heavy metals in acid mine drainage (AMD): assessment of the use of anodic stripping voltammetry.

We assessed the use of anodic stripping voltammetry (ASV) for in-situ determinations of both total concentration and speciation of dissolved heavy metals (Cd, Cu, Pb and Zn) in acid mine drainage (AMD). In the Kwangyang Au-Ag mine area of South Korea, different sites with varying water chemistry within an AMD were studied with a field portable anodic stripping voltammeter. Anodic stripping voltammetry after wet oxidation (acidification) was very sensitive enough to determine total concentration of dissolved Cd because Cd was dominantly present as 'labile' species, whilst the technique was not so effective for determining total Cu especially in the downstream sites from the retention pond, due to its complexation with organic matter. For dissolved Pb, the concentrations determined by ASV after wet oxidation generally agreed with those by ICP-AES. In the downstream samples (pH>5), however, ASV data after wet oxidation were lower than ICP-AES data because a significant fraction of dissolved Pb was present in those samples as 'inert' species associated with colloidal iron oxide particles. The determination of total dissolved Zn by ASV after wet oxidation appeared to be unsatisfactory for the samples with high Cu content, possibly due to the interference by the formation of Zn-Cu intermetallic compounds on the mercury coated electrode. In AMD samples with high dissolved iron, use of ultraviolet irradiation was not effective for determining total concentrations because humate destruction by UV irradiation possibly resulted in the removal of a part of dissolved heavy metals from waters through the precipitation of iron hydroxides.